EP0342652A2 - Thermoplastic wholly aromatic copolyimide ester and process for producing the same - Google Patents

Thermoplastic wholly aromatic copolyimide ester and process for producing the same Download PDF

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Publication number
EP0342652A2
EP0342652A2 EP89108880A EP89108880A EP0342652A2 EP 0342652 A2 EP0342652 A2 EP 0342652A2 EP 89108880 A EP89108880 A EP 89108880A EP 89108880 A EP89108880 A EP 89108880A EP 0342652 A2 EP0342652 A2 EP 0342652A2
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represented
iii
mole ratio
general formula
following general
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EP89108880A
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German (de)
French (fr)
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EP0342652B1 (en
EP0342652A3 (en
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Hideo Hayashi
Makoto Wakabayashi
Kenichi Fujiwara
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Idemitsu Petrochemical Co Ltd
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Idemitsu Petrochemical Co Ltd
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Priority claimed from JP11835588A external-priority patent/JPH0816155B2/en
Priority claimed from JP12504988A external-priority patent/JPH0689143B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides

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  • the present invention relates to thermoplastic wholly aromatic copolyimide esters having excellent dimensional stability and to processes for producing the same. More particularly, the present invention relates to novel thermoplastic wholly aromatic copolyimide esters and processes for producing the same which may be suitably used for electric or electronic parts, etc., which require heat resistance and excellent dimensional precision and dimensional accuracy in both flow direction (machine direction: MD) and a direction making a right angle with the flow direction (transverse direction: TD).
  • MD machine direction
  • TD transverse direction
  • thermoplastic resins having extremely small coefficients of linear expansion in MD have come to be known. These resins are a series of resins called thermotropic liquid-crystalline polymers, and some examples of such resins are the wholly aromatic copolyesters disclosed in Japanese Patent Application Laid- open No. 54-77691.
  • polyesters have small coefficients of linear expansion in MD, they are yet unsatisfactory in dimensional stability because their coefficients of linear expansion in TD are much the same as those of common thermoplastic resins.
  • polyimide esters containing both imide bonds and ester bonds in their polymer molecules have been well known.
  • those having excellent, heat resistance are disclosed in U.S. Pat. No. 3,542,731, those improved in heat resistance, mechanical properties, and processability in Japanese Patent Application Laid-open No. 58-67725, those having high moduluses of elasticity in Japanese Patent Application Laid-open No. 55-84326, those having high toughness in Japanese Patent Application Laid-open No. 58-113222, and those having high rigidity in Japanese Patent Application Laid-open No. 60-4531.
  • these polyimide esters are also hardly satisfactory in dimensional stability.
  • An object of the present invention is to provide a novel thermoplastic wholly aromatic copolyimide ester having excellent dimensional stability and dimensional precision in both MD and TD.
  • Another object of the present invention is to provide a process which is particularly advantageous for practical production of the thermoplastic wholly aromatic copolyimide esters having the excellent properties described above.
  • thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: the recurring unit (II) represented by the following general formula: wherein
  • This invention also provides a process for the preparation of such thermoplastic wholly aromatic copolyimide ester.
  • the recurring unit (I) in the copolyimide ester of the invention is
  • the recurring unit (II) is, concretely,
  • the preferred copolyimide ester contains the recurring unit (II) of or contains as the main component of the recurring unit (II).
  • thermoplastic wholly aromatic copolyimide ester of the present invention may contain either one of them or both of them in a desired ratio.
  • the recurring unit (III) is, concretely, Preferably, the copolyimide ester of the present invention contains 2 to 22 mole % of the recurring unit represented by the following formula:
  • the copolyimide ester of the present invention may contain either one of them or both of them in a desired ratio.
  • the recurring unit (IV 1) is, concretely, or
  • the copolyimide ester of the present invention may contain either one of them or two or more of them in a desired ratio.
  • the copolyimide ester of the present invention has the melt viscosity of the above-described range. If the melt viscosity deviates the above-described range, the thermoplasticity will be insufficient for molding the obtained copolyimide ester easily by injection molding or the like, or the mechanical properties or heat resistance will become insufficient.
  • thermoplastic wholly aromatic copolyimide ester of the present invention include those consisting essentially of the recurring unit (I) represented bythe following formula: the recurring unit (II) represented by the following general formula: wherein
  • thermoplastic wholly aromatic copolyimide ester of the present invention also include those consisting essentially of the recurring unit (I) represented by the following formula: the recurring unit (II) represented by the following general formula: wherein
  • the method of producing the preferred thermoplastic wholly aromatic copolyimide esters of the present invention is not particularly limited, it is preferable to produce the copolyimide esters containing the recurring unit (IV 1) by employing the processes of the present invention, which is particularly advantageous in practical production.
  • the processes of the present invention for producing the copolyimide esters containing the recurring unit (IV 1) comprise reacting at least three kinds of particular phenylene aromatic compounds with a particular pyromellitimide aromatic compound or with a pyromellitamide aromatic compound, which is a precursor of the former, in a particular ratio, to carry out polyester condensation thereof or imide-cyclization and polyester condensation thereof.
  • the present invention provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: the recurring unit (II) represented by the following formula: wherein
  • thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: the recurring unit (II) represented by the following general formula: wherein
  • the copolyimide esters containing the recurring unit (IV 2) by employing the processes of the present invention, which is particularly advantageous in practical production.
  • the process of the present invention for producing the copolyimide esters containing the recurring unit (IV 2) comprises reacting at least three kinds of particular phenylene aromatic compounds and a particular phthalimide aromatic compound or phthalamide aromatic compound, which is a precursor of the former, in a particular ratio to carry out polyester condensation thereof or imide-cyclization and polyester condensation thereof.
  • the present invention further provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: - the recurring unit (II) represented by the following general formula: wherein
  • the present invention further provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: the recurring unit (II) represented by the following general formula: wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently a hydrocarbon group of 1 to 18 carbon atoms, and some illustrative examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, heptyl, isooctyl, nonyl, decyl, pentadecyl, and heptadecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl or aralkyl groups such as phenyl, tolyl, naphthyl, and benzyl.
  • the particularly preferred is methyl group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 may be identical with each other or may include some being identical with each other and the others being different from each other, or all of them may be different from each other. The same may be said of R 1 , R 2 , R 3 , R 6 , and R 7 .
  • Z 1 , Z 2 , and Z 3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and some illustrative examples of the hydrocarbon group include the same hydrocarbon groups as described above.
  • the particularly preferred are hydrogen atom, methyl, etc.
  • Z 1 , Z 2 , and Z 3 may be identical with each other or may include some different groups, or all of them may be different from each other.
  • Z 4 and Z 5 are hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms when m is an integer of 1, and some illustrative examples of the hydrocarbon group include the same hydrocarbon groups as listed above.
  • the particularly preferred are hydrogen atom and methyl group.
  • the examples of the compound (I') include 4-hydroxybenzoic acid, 4-acyloxybenzoic acids prepared by acylating 4-hydroxybenzoic acid with R 1 COOH or a derivative thereof (R 1 is defined above.), and-4-hydroxybenzoic esters and 4-acyloxybenzoic esters prepared respectively by esterifying 4-hydroxybenzoic acid or the acyloxybenzoic acids with Z 1 OH (Z 1 is as defined above.).
  • Some illustrative examples of the compound (I') include 4-hydroxybenzoic acid, 4-hydroxybenzoic esters such as methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, and benzyl 4-hydroxybenzoate, 4-acyloxybenzoic acids such as 4-acetoxybenzoic acid and 4-benzoyloxybenzoic acid, and 4-acyloxybenzoic esters such as methyl 4-acetoxybenzoate, butyl 4-acetoxybenzoate, and benzyl 4-acetoxybenzoate.
  • 4-hydroxybenzoic acid 4-hydroxybenzoic esters such as methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, and benzyl 4-hydroxybenzoate
  • 4-acyloxybenzoic acids such as 4-acetoxybenzoic acid and 4-benzoyloxybenzoic acid
  • the preferred examples include 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, 4-acetoxybenzoic acid, and methyl 4-acetoxybenzoate, and the. particularly preferred examples include 4-hydroxybenzoic acid and 4-acetoxybenzoic acid.
  • These compounds may be used individually or in a combination of two or more of them.
  • the examples of the compound (II') include hydroquinone, 4,4 -dihydroxybiphenyl, and the compounds prepared by acylating each of them with R 2 COOH, R 3 COOH (R 2 and R 3 are as defined above.) or a derivative thereof.
  • Some illustrative examples of the compound (II') include hydroquinone, 4-acyloxyphenols such as 4-acetoxyphenol, 4-benzoyloxyphenol, and 4-propionyloxyphenol, 1,4-diacyloxybenzenes such as 1,4-diacetoxybenzene, 4,4 -dihydroxybiphenyl, 4 -acyloxy-4-hydroxybiphenyls such as 4 -acetoxy-4-hydroxybiphenyl, and 4,4 -diacyloxybiphenyls such as 4,4 -diacetoxybiphenyl.
  • hydroquinone 4-acyloxyphenols such as 4-acetoxyphenol, 4-benzoyloxyphenol, and 4-propionyloxyphenol
  • 1,4-diacyloxybenzenes such as 1,4-diacetoxybenzene
  • 4,4 -dihydroxybiphenyl 4,4 -dihydroxybiphenyl
  • the preferred examples include hydroquinone, 4-acetoxyphenol, 1,4-diacetoxybenzene, 4,4 -dihydroxybiphenyl, 4 - acetoxy-4-hydroxybiphenyl, and 4,4 -diacetoxybiphenyl.
  • the particularly preferred examples include hydroquinone, 4,4 -dihydroxybiphenyl, and 4,4 -diacetoxybiphenyl.
  • These compounds may be used individually or in a combination of two or more of them.
  • the examples of the compound (III') include terephthalic acid, isophtahlic acid, and the compounds prepared by esterifying each of them with Z 2 OH or Z 3 0H (Z 2 and Z 3 are as difined above.).
  • Some illustrative examples of the compound (III') include terephthalic acid, isophthalic acid, terephthalic monoesters such as monomethyl terephthalate, monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, monohexyl terephthalate, and monobenzyl terephthalate, terephthalic diesters such as dimethyl terephthalate and diethyl terephthalate, isophthalic monoesters such as monomethyl isophthalate, monoethyl isophthalate, monopropyl isophthalate, monobutyl isophthalate, monohexyl isophthalate, monooctyl isophthalate, monodecyl isophthalate, and monobenzyl isophthalate, isophthalic diesters such as dimethyl isophthalate, diethyl isophthalate, and dibutyl isophthalate.
  • the preferred examples include
  • These compounds may be used individually or in a combination of two or more of them.
  • the examples of the compound (IV 1 wherein m is 1 include N,N' -bis(4-carboxyphenyl)pyromellitimide;
  • the preferred examples include N,N' -bis(4-carboxyphenyl)pyromellitimide, N,N' -bis(3-carboxyphenyl)pyromellitimide, N,N -bis(4-hydroxyphenyl)pyromellitimide, and N,N' -bis(3-hydroxyphenyl)-pyromellitimide.
  • the particularly preferred examples include N,N -bis(4-carboxyphenyl)pyromellitimide and N,N' -bis(4-hydroxyphenyl)pyromeilitimide.
  • These compounds may be used individually or in a combination of two or more of them.
  • the particularly preferred examples include
  • These compounds may be used individually or in a form of a mixture of two or more of them.
  • the above-described compound (IV 1'') may be synthesized, for example, by the reaction of a compound (A) (pyromellitic anhydride) represented by the following formula: with at least one compound (B) (p- or m-aminobenzoic acid or an ester thereof, or p- or m-aminophenol or p- or m-acyloxyaniline) represented by the following general formula: wherein
  • the synthesized compound (IV 1 will be generally a mixture of the compound represented by the general formula (IV1 a) and the compound represented by the general formula (IV1 b).
  • the compound (IV 1') may be prepared, for example, by the dehydration-cyclization (imide-cyclization) of the compound (IV 1 synthesized by the above method.
  • the compound (IV 1'') may be prepared by the hydrolysis of the compound (IV 1 ).
  • the reaction of the compound (A) with the compound (B) easily proceeds merely by mixing both compounds, preferably in a molten state, forming a nonsoluble amide acid, i.e. the compound (IV 1 ''), which generally precipitates. Though the reaction proceeds efficiently at room temperature, the preferable reaction temperature ranges from - 50 °C to 100° C, and, in many cases, temperatures of 0 to 80 °C are suitable for the reaction. The reaction proceeds quickly and generally requires no particular catalyst.
  • the dehydration-cyclization of the compound (IV 1 may be carried out by various methods. Some illustrative examples of the methods include (1) a dehydration-cyclization in the presence of a carboxylic anhydride, (2) a dehydration-cyclization using an inorganic acid or a condensation product thereof having dehydrating function, (3) azeotropic dehydration-cyclization in the presence of an acid catalyst, (4) cyclization using a specific dehydration agent, and (5) dehydration-cyclization by heating.
  • those wherein Z 4 and Z 5 are groups other than hydrogen atom may be prepared by a reaction using the raw material compounds (IV 1 ) each having the corresponding substituent, or may be derived from the compounds (IV 1 wherein Z 4 and Z 5 are hydrogen atom.
  • the examples of the compound (IV 2" ) include the compounds represented by the following general formulas.
  • the phthalimide compound (IV 2' ) may be prepared by reacting a derivative of hydroxyphthalic acid represented by the following general formula: wherein Y is Y 4 or Y 5 , and Y 4 and Y 5 are as defined above and generally are identical with each other, with p-phenylenediamine represented by the following formula: to form the amide acids represented by the above general formulas (IV 2 a), (IV 2 b) or (IV 2 c), followed by dehydrating and cyclizing the obtained amide acids.
  • the reaction of the compound (C) with p-phenylenediamine easily proceeds merely by mixing both the compounds, preferably in a molten state, forming a nonsoluble amide acid which generally precipitates. Though the reaction proceeds efficiently at room temperature, the preferable reaction temperature ranges from - 50 °C to 100°C and in many cases, temperatures of 0 to 80° C are suitable for the reaction. The reaction proceeds quickly and generally requires no particular catalyst.
  • the dehydration-cyclization of the amide acids represented by the formulas (IV 2 a) (IV 2 b), and (IV 2 c) may be carried out by various methods. Some illustrative examples of the methods include those described as the examples of the dehydration-cyclization methods for the compound (IV 1 '').
  • those wherein Y 4 and Y 5 are groups other than hydrogen atom may be prepared by a reaction using the raw material compounds (IV 2" ) each having the corresponding substituent, or may be derived from the compounds (IV 2') wherein Y 4 and Y 5 are hydrogen atom.
  • the reaction of the above-described compounds (I ), (II' ), (III' ), and (IV 1') or (IV 2') is carried out generally at 200 to 400 °C preferably 230 to 370° C, generally at atmospheric pressure or below, and in the latter half of the reaction, preferably at a vacuum of 300 to 0.01 Torr.
  • the reaction time varies generally from several minutes to tens of hours depending upon the objective melt viscosity of the polymer. In order to prevent the degradation of the polymer at the reaction temperature, it is preferable to restrict the reaction time to from minutes to hours.
  • catalyst is not particularly necessary for the above-described reaction, a proper polycondensation catalyst such as antimony oxide and germanium oxide may be used.
  • reaction materials all of them may be mixed together from the beginning of the reaction, or each reaction material may be added at a separate reaction stage.
  • the compound (I' ) may be added after the mixture of the compounds (II' ), (III' ), and (IV 1' ) or (IV 2 ) has been reacted to same degree.
  • separation in the addition of the reaction materials makes it easier easity to control the distribution of the components of the copolyimide ester, from random copolyester to block copolyester.
  • reaction is conducted as described above and is concluded by eliminating at least the compound (V' ) (when m is 1), or the compound (VI') and the compound (VII') (when m is 0), or the compound (VIII'
  • reaction of the compounds (I ), (II'), (III and (IV 1 or (IV 2'') may be carried out by the similar procedure to the reaction of the compounds (I' ), (II' ), (III' ), and (IV 1') or (IV 2') with the exception that the compounds (IV 1 ) or (IV 2' ) are replaced by the compounds (IV 1'') or (IV 2 ) and imidecyclization is further carried out.
  • reaction described above is generally carried out without particular solvent, a suitable solvent may also be used if desired.
  • the copolyimide ester of the present invention can be prepared.
  • the obtained polymer if necessary, may be further subjected to after-treatments, such as a known purification, to collect it as a polymer of a desired purity.
  • copolyimide ester of the present invention can be suitably produced by the above procedure.
  • the copolyimide ester of the present invention may be injection-molded at general molding temperatures (not higher than 400 C) and, also, may be molded by any molding technique employed for molding common thermoplastic resins, such as extrution molding, compression molding, and spinning. Further, the obtained molds may be heat treated at an appropriate temperature for an appropriate time.
  • the copolyimide ester of the present invention is, therefore, a novel thermoplastic polymer which has excellent dimensional stability and dimensional precision in both MD and TD and, as well, excels in heat resistance, mechanical properties, etc. Accordingly, the copolyimide ester of the present invention is useful as materials in various fields, for example, as the material for precision-injection molded parts such as electric or electronic parts which require heat resistance and dimensional precision, filament, film, or sheet.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the polymer had a melt viscosity of 130 Pa•s at 380°C
  • the polymer exhibited optical anisotropy even in molten state.
  • the observation of the optical anisotropy was conducted with a polarizing microscope produced by Nikon Co., Ltd. equipped with a hot stage produced by Lincam Co., Ltd.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 75 Paes at 380°C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 240 Pa•s at 390 C.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 150 Pa.s at 320 °C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 215 Pa•s at 380°C.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 220 Paes at 380°C.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 175 Pa•s at 380°C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the polymer had a melt viscosity of 320 Pa*s at 350° C and exhibited optical anisotropy even in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 230 Pa•s at 380°C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 170 Paes at 330°C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 210 Paes at 320 °C.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 180 Paes at 32 C
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 200 Pa ⁇ s at 330°C.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 140 Paes at 340°C.
  • the polymer exhibited optical anisotropy in molten state.
  • Example 2 the measurement procedures of Example 1 were repeated with the exception that the copolyimide ester prepared in Example 1 was replaced by a commercial poly- butyleneterephthalate (Duranex 2000 produced by Celanese Co., Ltd., Comparative Example 1), a commercial polycarbonate (A 2200 produced by Idemitsu Petrochemical Co., Ltd., Comparative Example 2), a commercial polyether imide (Ultem 1000 produced by General Electric Company, Comparative Example 3), a commercial thermotropic iiquid-crystalline copolyester (Ekonol E 6000 produced by SUMITOMO CHEMICAL CO., LTD., Comparative Example 4), or a commercial thermotropic liquid-crystalline copolyester (Vectra A 950 produced by Celanese Co., Ltd., Comparative Example 5), respectively.
  • a commercial poly- butyleneterephthalate Duranex 2000 produced by Celanese Co., Ltd., Comparative Example 1
  • a 2200 produced by Idemitsu Petrochemical Co., Ltd., Compar
  • the molding was conducted by using an injection molder (Toshiba IS 45 P) at a molding temperature of 250 to 350 C and at a mold temperature of 120" C
  • the measurement of coefficient of linear expansion was conducted in compression mode by using Seiko Thermal Analysis Apparatuses SSC-300 and TMA-100 on a test piece of about 10 (measuring direction)x 5x 1.6 mm cut out from the center portion of a plate of 63.5x 63.5x 1.6 mm, under a load of 5 g, at a temperature raising rate of 10°C /min.
  • the measurement of heat distortion temperature was conducted on a test piece of 127x 12. 7x 3.2 mm under a load of 18.6 kg/cm 2 using an apparatus produced by Toyo Seiki Co., Ltd.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 280 Paes at 380°C
  • the polymer exhibited optical anisotropy even in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 340 Pa ⁇ s at 380 C .
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 300 Pass at 380 °C.
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 380 Pa ⁇ s at 380°C .
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 270 Pa ⁇ s at 380 C .
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 370 Pa ⁇ s at 380 °C.
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 300 Pa ⁇ s at 380 °C .
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.
  • the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
  • the melt viscosity of the polymer was measured by the same method as Example 1 to be 310 Pa ⁇ s at 380 °C.
  • the properties of the polymer are shown in Table 2.
  • the polymer exhibited optical anisotropy in molten state.

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Abstract

A thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imga0001
the recurring unit (II) represented by the following general formula:
Figure imga0002
wherein
  • n is an integer of 0 or 1;
  • the recurring unit (III) represented by the following formula:
    Figure imga0003
    wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
  • and the recurring units (IV 1) or (IV 2) represented respectively by the following formulas:
    Figure imga0004
    wherein
    • -Q- is -0- or -CO-
    • and each Q is present at para position or meta position of the benzene nucleus respectively to the imide group,
    • or
      Figure imga0005
      with the proviso that the recurring units (I), (II), (III), and (IV) are bonded to form ester bonds,
    • and wherein the thermoplastic wholly aromatic copolyimide ester has a melt viscosity of from 1.0 to 1.0 x 105 Pa•s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400° C

Description

    BACKGROUND OF THE INVENTION (a) Field of the Invention
  • The present invention relates to thermoplastic wholly aromatic copolyimide esters having excellent dimensional stability and to processes for producing the same. More particularly, the present invention relates to novel thermoplastic wholly aromatic copolyimide esters and processes for producing the same which may be suitably used for electric or electronic parts, etc., which require heat resistance and excellent dimensional precision and dimensional accuracy in both flow direction (machine direction: MD) and a direction making a right angle with the flow direction (transverse direction: TD).
    • (b) Description of the Related Art
  • In recent years, thermoplastic resins having extremely small coefficients of linear expansion in MD have come to be known. These resins are a series of resins called thermotropic liquid-crystalline polymers, and some examples of such resins are the wholly aromatic copolyesters disclosed in Japanese Patent Application Laid- open No. 54-77691.
  • Although these polyesters have small coefficients of linear expansion in MD, they are yet unsatisfactory in dimensional stability because their coefficients of linear expansion in TD are much the same as those of common thermoplastic resins.
  • Also, polyimide esters containing both imide bonds and ester bonds in their polymer molecules have been well known. For example, those having excellent, heat resistance are disclosed in U.S. Pat. No. 3,542,731, those improved in heat resistance, mechanical properties, and processability in Japanese Patent Application Laid-open No. 58-67725, those having high moduluses of elasticity in Japanese Patent Application Laid-open No. 55-84326, those having high toughness in Japanese Patent Application Laid-open No. 58-113222, and those having high rigidity in Japanese Patent Application Laid-open No. 60-4531. However, these polyimide esters are also hardly satisfactory in dimensional stability.
    • SUMMARY OF THE INVENTION
  • An object of the present invention is to provide a novel thermoplastic wholly aromatic copolyimide ester having excellent dimensional stability and dimensional precision in both MD and TD.
  • Another object of the present invention is to provide a process which is particularly advantageous for practical production of the thermoplastic wholly aromatic copolyimide esters having the excellent properties described above.
  • That is, the present invention provides a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
    Figure imgb0001
    the recurring unit (II) represented by the following general formula:
    Figure imgb0002
    wherein
    • n is an integer of 0 or 1;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0003
      wherein
      the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring units (IV 1) or (IV 2) represented respectively by the following general formulas;
      Figure imgb0004
      wherein
      • -Q- is -O- or -CO-
      • and each Q is present at para position or meta position of the benzene nucleus respectively to the imide group,
      • or
        Figure imgb0005
        with the proviso that the recurring units (I), (II), (III), and (IV 1) or (IV 2) are bonded to form ester bonds,
      • and wherein the thermoplastic wholly aromatic copolyimide ester has a melt viscosity of from 1.0 to 1.0 x 105 Paes as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400° C
  • This invention also provides a process for the preparation of such thermoplastic wholly aromatic copolyimide ester.
    • BRIEF DESCRIPTION OF THE INVENTION
    • Fig. 1 is an infrared spectrum of the copolyimide ester obtained in Example 3.
    • Fig. 2 is an infrared spectrum of the copolyimide ester obtained in Example 9.
    • Fig. 3 is an infrared spectrum of the copolyimide ester obtained in Example 21.
    DESCRIPTION OF THE PREFERRED EMBODIMENT
  • The recurring unit (I) in the copolyimide ester of the invention is
    Figure imgb0006
  • The recurring unit (II) is, concretely,
    Figure imgb0007
    The preferred copolyimide ester contains the recurring unit (II) of
    Figure imgb0008
    or contains
    Figure imgb0009
    as the main component of the recurring unit (II).
  • The thermoplastic wholly aromatic copolyimide ester of the present invention (hereinafter referred to occasionally as copolyimide ester) may contain either one of them or both of them in a desired ratio.
  • The recurring unit (III) is, concretely,
    Figure imgb0010
    Preferably, the copolyimide ester of the present invention contains 2 to 22 mole % of the recurring unit represented by the following formula:
    Figure imgb0011
  • The copolyimide ester of the present invention may contain either one of them or both of them in a desired ratio.
  • The recurring unit (IV 1) is, concretely,
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    Figure imgb0016
    or
    Figure imgb0017
  • The copolyimide ester of the present invention may contain either one of them or two or more of them in a desired ratio.
  • The copolyimide ester of the present invention has the melt viscosity of the above-described range. If the melt viscosity deviates the above-described range, the thermoplasticity will be insufficient for molding the obtained copolyimide ester easily by injection molding or the like, or the mechanical properties or heat resistance will become insufficient.
  • The examples of the preferred thermoplastic wholly aromatic copolyimide ester of the present invention include those consisting essentially of the recurring unit (I) represented bythe following formula:
    Figure imgb0018
    the recurring unit (II) represented by the following general formula:
    Figure imgb0019
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0020
      wherein
      the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 1) represented by the following general formula;
      Figure imgb0021
      wherein
      -Q- is as defined above;
    • and wherein when -Q- is -CO-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (III)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(III)+(IV 1)] is from (10/11) to (11/10), and when -Q- is -0-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II)+(IV 1)] is from (10/11) to (11/10).
  • The examples of the preferred thermoplastic wholly aromatic copolyimide ester of the present invention also include those consisting essentially of the recurring unit (I) represented by the following formula:
    Figure imgb0022
    the recurring unit (II) represented by the following general formula:
    Figure imgb0023
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0024
       wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 2) represented by the following general formula;
      Figure imgb0025
    • and wherein the mole ratio of (I)/[(II) + (III) + (IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1 and the mole ratio of (III)/[(II)+(IV 2)] is from (10/11) to (11/10).
  • If the ratios of the recurring units deviate from the ranges of the above-described mole ratios, it may sometimes become difficult to attain the desired dimensional stability or dimensional precision.
  • Although the method of producing the preferred thermoplastic wholly aromatic copolyimide esters of the present invention is not particularly limited, it is preferable to produce the copolyimide esters containing the recurring unit (IV 1) by employing the processes of the present invention, which is particularly advantageous in practical production. The processes of the present invention for producing the copolyimide esters containing the recurring unit (IV 1) comprise reacting at least three kinds of particular phenylene aromatic compounds with a particular pyromellitimide aromatic compound or with a pyromellitamide aromatic compound, which is a precursor of the former, in a particular ratio, to carry out polyester condensation thereof or imide-cyclization and polyester condensation thereof.
  • That is, the present invention provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
    Figure imgb0026
    the recurring unit (II) represented by the following formula:
    Figure imgb0027
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0028
      wherein
      the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 1) represented by the following general formula:
      Figure imgb0029
      wherein
      -Q- is as defined above;
    • with the proviso that the recurring units (I), (II), (III), and (IV 1) are bonded to form ester bonds and that when -Q-is -CO-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (III)-/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(III)+(IV 1)] is from (10/11) to (11/10), and when -Q- is -0-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II)+(IV 1)] is from (10/11) to (11/10);
    • and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa•s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400 °C,
      which process comprises:
      • reacting a compound (I') represented by the following general formula:
        Figure imgb0030
        wherein
        • Y1 is hydrogen atom or R1CO-, R1 being a hydrocarbon group of 1 to 18 carbon atoms, and
        • Z1 is hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms;
    • a compound (II') represented by the following general formula:
      Figure imgb0031
      wherein
      • n is an integer of 0 or 1,
      • Y2 is hydrogen atom or R2CO-, and
      • Y3 is hydrogen atom or R3CO-,
      • R2 and R3 being independently a hydrocarbon group of 1 to 18 carbon atoms;
    • a compound (III') represented by the following general formula:
      Figure imgb0032
      wherein
      • Z2 and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and the - C - O-Z3
      • group is present at para position or meta position of the benzene nucleus to the Z2-0- C - group;
    • and the compound (IV 1') represented by the following general formula:
      Figure imgb0033
      wherein
      • m is an integer of 0 or 1,
      • Z4 is, when m =0, hydrogen atom or R4-CO-, R4 being a hydrocarbon group of 1 to 18 carbon atoms or, when m = 1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, Z5 is, when m=0, hydrogen atom or R5-CO-, R5 being a hydrocarbon group of 1 to 18 carbon atoms or, when m = 1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms,
      • Z4-O(̵C )̵m is present at para position or meta position of the benzene nucleus to the imide group, and
      • (̵C)̵m O-Z5 is present at para position or meta position of the benzene nucleus to the imide group;
    • in such amounts as satisfy, when m = 1, a mole ratio of (I' )/[(II') + (III') + (IV 1' )] of from (20/80) to (90/10), a mole ratio of (III )/(IV 1') of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (II')/[(III') +(IV 1')] of from (10/11) to (11/10) or, when m=0, a mole ratio of (I' )/[(II') +(III' )+(IV 1')] of from (20/80) to (90/10), a mole ratio of (II')/(IV 1') of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III')/[(II') +(IV 1')] of from (10/11) to (11/10), so that when m = 1, then a compound (V ) represented by the following general formula:
      • Yp-O-Zq (V')
      wherein
      • YP is Y1, Y2 or Y3 and
      • Zq is Z1, Z2, Z3, Z4 or ZS,

      is eliminated, or, when m=0, then a compound (VI') represented by the following general formula:
      • Yp-O-Zs (VI')

      wherein
      • YP is as defined above and
      • Zs is Z1, Z2 or Z3,

      and a compound (VII') represented by the following general formula:
    • Zr-O-Zs (VII')

    wherein
    • Zs is as defined above and
    • Zr is Z4 or Z5.

    are eliminated.
  • Also the present invention provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
    Figure imgb0034
    the recurring unit (II) represented by the following general formula:
    Figure imgb0035
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0036
      wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 1) represented by the following general formula:
      Figure imgb0037
      wherein
      • -Q- is as defined above;
      • with the proviso that the recurring units (I), (II), (III), and (IV 1) are bonded to form ester bonds and that when -Q-is -CO-, then the mole ratio of (I)/[ (II)+(III)+(IV 1)] is from (20/80) to (90/10), the mole ratio of (III)-/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(III)+(IV 1)] is from (10/11) to (11/10), and when -Q- is -0-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to 90/10), the mole ratio of (II)/(IV) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III/[(II)+(IV 1)] is from (10/11) to (11/10);
    • and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa•s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400° C, which process comprises:
      • reacting a compound (I') represented by the following general formula:
        Figure imgb0038
        wherein
        • Y1 and Z1 are as defined above;
      • a compound (II') represented by the following general formula:
        Figure imgb0039
        wherein
        • n, Y2, and Y3 are as defined above;
      • a compound (III') represented by the following general formula:
        Figure imgb0040
        wherein
        • Z2 and Z3,- C -O-Z3 group, and Z2-O- C - group are as defined above;
      • and a compound (IV 1") represented by the following general formulas:
        Figure imgb0041
        or
        Figure imgb0042
        wherein
        • m, Z4, Z5, Z4-O(̵C)̵m, and (̵C )̵m-O-Z5 are as defined above;
      • in such amounts as satisfy, when m = 1, a mole ratio of (I' )/[(II') + (III') + (IV 1" )] of from (20/80) to (90/10), a mole ratio of (III')/(IV 1'') of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (II')/[(III') +(IV 1 )] of from (10/11) to (11/10) or, when m=0, a mole ratio of (I )/[(II')+(III') +(IV 1 )] of from (20/80) to (90/10), a mole ratio of (II')/(IV 1'' of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III')/[(II') +(IV 1'' )] of from (10/11) to (11/10),
      • so that the compound (IV 1 ) is imide-cyclized and, when m is 1, then a compound (V ) represented by the following general formula:
        • YP-O-Zq (V')

        wherein
        • YP is Y1, Y2 or Y3 and
        • Zq is Z1, Z2, Z3, Z4 or Z5,
        is eliminated,
      • or, when m is 0, then a compound (VI') represented by the following general formula:
        • Yp-O-Zs (VI')

        wherein
        • YP is as defined above and
        • Zs is Z1, Z2 or Z3,
      • and a compound (VII') represented by the following general formula:
        • Zr-O-Zs (VII')

        wherein
        • ZS is as defined above and
        • Zr is Z4 or Z5,

        are eliminated.
  • Also, it is preferable to produce the copolyimide esters containing the recurring unit (IV 2) by employing the processes of the present invention, which is particularly advantageous in practical production. The process of the present invention for producing the copolyimide esters containing the recurring unit (IV 2) comprises reacting at least three kinds of particular phenylene aromatic compounds and a particular phthalimide aromatic compound or phthalamide aromatic compound, which is a precursor of the former, in a particular ratio to carry out polyester condensation thereof or imide-cyclization and polyester condensation thereof.
  • That is, the present invention further provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula: -
    Figure imgb0043
    the recurring unit (II) represented by the following general formula:
    Figure imgb0044
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0045
      wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 2) represented by the following formula;
      Figure imgb0046
      with the proviso that the recurring units (I), (II), (III), and (IV 2) are bonded to form ester bonds and that the mole ratio of (I)/[(II) + (III) + (IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/((II)+(IV 2)] is from (10/11) to (11 /10);
    • and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa.s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400° C , which process comprises:
      • reacting a compound (I') represented by the following general formula:
        Figure imgb0047
        wherein
        • Y1 and Z1 are as defined above;
    • a compound (II') represented by the following general formula:
      Figure imgb0048
      wherein
      • n, Y2, and Y3 are as defined above;
    • a compound (III') represented by the following general formula:
      Figure imgb0049
      wherein
      • Z2, Z3, - C -O-Z3 group, and Z2-O- C group are as defined above;
    • and the compound (IV 2 ) represented by the following general formula:
      Figure imgb0050
      wherein
      • Y4 is hydrogen atom or R6-CO- and
      • Y5 is hydrogen atom or R7-CO-, R6 and R7 being independently a hydrocarbon group of 1 to 18 carbon atoms;
    • in such amounts as satisfy a mole ratio of (I' )/[(II') +(III') +(IV 2' )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 2' ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III )/[(II')+ (IV 2' )] of from (10/11) to (11/10),
      so that a compound (VIII') represented by the following general formula:
      • Yt-O-Zu (VIII')

      wherein
      • Yt is Y1, Y2, Y3, Y4 or Y5 and
      • Zu is Z1, Z2 or Z3,

      is eliminated.
  • Also, the present invention further provides a process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
    Figure imgb0051
    the recurring unit (II) represented by the following general formula:
    Figure imgb0052
    wherein
    • n is as defined above;
    • the recurring unit (III) represented by the following formula:
      Figure imgb0053
      wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
    • and the recurring unit (IV 2) represented by the following formula;
      Figure imgb0054
      with the proviso that the recurring units (I), (II), (III), and (IV 2) are bonded to form ester bonds and that the mole ratio of (I)/[(II)+(III)+(IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III/[(II)+(IV 2)] is from (10/11) to (11/10);
    • and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa•s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400 °C which process comprises:
      • reacting a compound (I') represented by the following general formula:
        Figure imgb0055
        wherein
        • Y1 and Z1 are as defined above;
    • a compound (II') represented by the following general formula:
      Figure imgb0056
      wherein
      • n, Y2, and Y3 are as defined above;
    • a compound (III') represented by the following general formula:
      Figure imgb0057
      wherein
      Figure imgb0058
      group are as defined above;
    • and a compound (IV 2'') represented by the following general formula:
      Figure imgb0059
      wherein
      • Y4 and Y5 are as defined above and
      • each Y4O- and -OY5 is present at para position or meta position of the benzene nucleus respectively to the amido group;
    • in such amounts as satisfy a mole ratio of (I )/[(II') +(III') +(IV 2" )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 2" ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III' )/[(II') + (IV 2" )] of from (10/11) to (11/10),
      so that the compound (IV 2'') is imide-cyclized and a compound (VIII') represented by the following general formula:
      • Yt-O-Zu (VIII')

      wherein
      • Yt is Y1, Y2, Y3, Y4 or Y5 and
      • Zu is Z1,Z2 or Z3,

      is eliminated.
  • Hereinafter, the processes of the present invention will be described in detail.
  • The above-described R1, R2, R3, R4, R5, R6, and R7 are independently a hydrocarbon group of 1 to 18 carbon atoms, and some illustrative examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, heptyl, isooctyl, nonyl, decyl, pentadecyl, and heptadecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl or aralkyl groups such as phenyl, tolyl, naphthyl, and benzyl. Among these, the particularly preferred is methyl group.
  • R1, R2, R3, R4, and R5 may be identical with each other or may include some being identical with each other and the others being different from each other, or all of them may be different from each other. The same may be said of R1, R2, R3, R6, and R7.
  • The above-described Z1, Z2, and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and some illustrative examples of the hydrocarbon group include the same hydrocarbon groups as described above. The particularly preferred are hydrogen atom, methyl, etc. Z1, Z2, and Z3 may be identical with each other or may include some different groups, or all of them may be different from each other.
  • Z4 and Z5 are hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms when m is an integer of 1, and some illustrative examples of the hydrocarbon group include the same hydrocarbon groups as listed above. The particularly preferred are hydrogen atom and methyl group.
  • The examples of the compound (I') include 4-hydroxybenzoic acid, 4-acyloxybenzoic acids prepared by acylating 4-hydroxybenzoic acid with R1COOH or a derivative thereof (R1 is defined above.), and-4-hydroxybenzoic esters and 4-acyloxybenzoic esters prepared respectively by esterifying 4-hydroxybenzoic acid or the acyloxybenzoic acids with Z1OH (Z1 is as defined above.).
  • Some illustrative examples of the compound (I') include 4-hydroxybenzoic acid, 4-hydroxybenzoic esters such as methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, and benzyl 4-hydroxybenzoate, 4-acyloxybenzoic acids such as 4-acetoxybenzoic acid and 4-benzoyloxybenzoic acid, and 4-acyloxybenzoic esters such as methyl 4-acetoxybenzoate, butyl 4-acetoxybenzoate, and benzyl 4-acetoxybenzoate.
  • Among these, the preferred examples include 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, 4-acetoxybenzoic acid, and methyl 4-acetoxybenzoate, and the. particularly preferred examples include 4-hydroxybenzoic acid and 4-acetoxybenzoic acid.
  • These compounds may be used individually or in a combination of two or more of them.
  • The examples of the compound (II') include hydroquinone, 4,4 -dihydroxybiphenyl, and the compounds prepared by acylating each of them with R2COOH, R3COOH (R2 and R3 are as defined above.) or a derivative thereof.
  • Some illustrative examples of the compound (II') include hydroquinone, 4-acyloxyphenols such as 4-acetoxyphenol, 4-benzoyloxyphenol, and 4-propionyloxyphenol, 1,4-diacyloxybenzenes such as 1,4-diacetoxybenzene, 4,4 -dihydroxybiphenyl, 4 -acyloxy-4-hydroxybiphenyls such as 4 -acetoxy-4-hydroxybiphenyl, and 4,4 -diacyloxybiphenyls such as 4,4 -diacetoxybiphenyl. Among these, the preferred examples include hydroquinone, 4-acetoxyphenol, 1,4-diacetoxybenzene, 4,4 -dihydroxybiphenyl, 4 - acetoxy-4-hydroxybiphenyl, and 4,4 -diacetoxybiphenyl. The particularly preferred examples include hydroquinone, 4,4 -dihydroxybiphenyl, and 4,4 -diacetoxybiphenyl.
  • These compounds may be used individually or in a combination of two or more of them.
  • The examples of the compound (III') include terephthalic acid, isophtahlic acid, and the compounds prepared by esterifying each of them with Z2OH or Z30H (Z2 and Z3 are as difined above.).
  • Some illustrative examples of the compound (III') include terephthalic acid, isophthalic acid, terephthalic monoesters such as monomethyl terephthalate, monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, monohexyl terephthalate, and monobenzyl terephthalate, terephthalic diesters such as dimethyl terephthalate and diethyl terephthalate, isophthalic monoesters such as monomethyl isophthalate, monoethyl isophthalate, monopropyl isophthalate, monobutyl isophthalate, monohexyl isophthalate, monooctyl isophthalate, monodecyl isophthalate, and monobenzyl isophthalate, isophthalic diesters such as dimethyl isophthalate, diethyl isophthalate, and dibutyl isophthalate. Among these, the preferred examples include terephthalic acid, dimethyl terephthalate, isophthalic acid, and dimethyl isophthalate. The particularly preferred examples include terephthalic acid and isophthalic acid.
  • These compounds may be used individually or in a combination of two or more of them.
  • Among the examples of the compound (IV 1 ), the examples of the compound (IV 1 wherein m is 1 include N,N' -bis(4-carboxyphenyl)pyromellitimide;
    • N-(4-carboxyphenyl or 4-alkoxycarbonylphenyl)-N' -(4-carboxyphenyl or 4-alkoxycarbonylphenyl)-pyromellitimide, such as N,N' -bis(4-methoxycarbonylphenyl)pyromellitimide, N,N -bis(4-ethoxycarbonyl- phenyl)pyromellitimide, and N-(4-carboxyphenyl)-N'-(4-methoxycarbonylphenyl)pyromellitimide;
    • N-(3-carboxyphenyl or 3-alkoxycarbonylphenyl)-N'-(3-carboxyphenyl or 3-alkoxycarbonylphenyl)-pyromellitimide, such as N,N -bis(3-carboxyphenyl)pyromellitimide, N,N -bis(3-methoxycarbonylphenyl)-pyromellitimide, and N-(3-carboxyphenyl)-N -(3-methoxycarbonylphenyl)pyromellitimide;
    • and N-(4-carboxyphenyl or alkoxycarbonylphenyl)-N'-(3-carboxyphenyl or alkoxycarbonylphenyl)-pyromellitimide, such as N-(4-carboxyphenyl)-N -(3-carboxyphenyl)pyromellitimide,
    • N-(4-methoxycarbonylphenyl)-N'-(3-methoxycarbonylphenyl)pyromellitimide, and
    • N-(4-carboxyphenyl)-N'-(3-methoxycarbonylphenyi)pyromellitimide, and the examples of the compound (IV 1 wherein m is 0 include
    • N-(4-hydroxyphenyl or 4-acyloxyphenyl)-N' -(4-hydroxyphenyl or 4-acyloxyphenyl)pyromellitimide, such as N,N' -bis(4-hydroxyphenyl)pyromellitimide, N,N' -bis(4-acetoxyphenyl)pyromellitimide, N,N' -bis(4-pro- pionyloxyphenyl)pyromellitimide, N,N -bis(4-benzoyloxyphenyi)pyromellitimide, and N-(4-hydroxyphenyl)-N' -(4-acetoxyphenyl)pyromellitimide; N-(3-hydroxyphenyl or 3-acyloxyphenyl)-N'-(3-hydroxyphenyl or 3-ac- yloxyphenyl)pyromellitimide, such as N,N -bis(3-hydroxyphenyl)pyromellitimide, N,N -bis(3-acetoxyphenyl)pyromellitimide, and N-(3-hydroxyphenyl)-N' -(3-acetoxyphenyl)pyromellitimide; and N-(4-hydroxyphenyl or 4-acyloxyphenyl)-N'-(3-hydroxyphenyl or 3-acyloxyphenyl)pyromellitimide, such as N-(4-hydroxyphenyl)-N' -(3-hydroxyphenyl)pyromellitimide, N-(4-acetoxyphenyl)-N' -(3-acetoxyphenyl)pyromellitimide, and N-(4-hydroxyphenyl)-N' -(3-acetoxyphenyl)pyromellitimide.
  • Among these, the preferred examples include N,N' -bis(4-carboxyphenyl)pyromellitimide, N,N' -bis(3-carboxyphenyl)pyromellitimide, N,N -bis(4-hydroxyphenyl)pyromellitimide, and N,N' -bis(3-hydroxyphenyl)-pyromellitimide.
  • The particularly preferred examples include N,N -bis(4-carboxyphenyl)pyromellitimide and N,N' -bis(4-hydroxyphenyl)pyromeilitimide.
  • These compounds may be used individually or in a combination of two or more of them.
  • Among the examples of the compound (IV 1''), some illustrative examples of the compound (IV 1'') wherein m is 1 include
    • 4,6-bis(4-carboxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4,6-bis(3-carboxyphenylaminocarbonyl )benzene-1,3-dicarboxylic acid,
    • 4,6-bis(4-methoxycarbonylphenylaminocarbonyl )benzene-1,3-dicarboxylic acid,
    • 4,6-bis(3-methoxycarbonylphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4-(4-carboxyphenylaminocarbonyl)-6-(3-carboxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 2,5-bis(4-carboxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid,
    • 2,5-bis(3-carboxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid,
    • 2,5-bis(4-methoxycarbonylphenylaminocarbonyl)benzene-1,4-dicarboxylic acid, and
    • 2-(3-carboxyphenylaminocarbonyl)-5-(4-carboxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid,
    • and some illustrative examples of the compound (IV 1'') wherein m is 0 include
    • 4,6-bis(4-hydroxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4,6-bis(3-hydroxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4,6-bis(4-acetoxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4,6-bis(3-acetoxyphenylaminocarbonyl)benzene-1,3-dicarboxyiic acid,
    • 4-(4-hydroxyphenylaminocarbonyl)-6-(3-hydroxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 2,5-bis(4-hydroxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid,
    • 2,5-bis(3-hydroxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid,
    • 2,5-bis(4-acetoxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid, and
    • 2-(3-hydroxyphenylaminocarbonyl)-5-(4-hydroxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid.
  • Among these, the particularly preferred examples include
    • 4,6-bis(4-carboxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 4,6-bis(4-hydroxyphenylaminocarbonyl)benzene-1,3-dicarboxylic acid,
    • 2,5-bis(4-carboxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid, and
    • 2,5-bis(4-hydroxyphenylaminocarbonyl)benzene-1,4-dicarboxylic acid.
  • These compounds may be used individually or in a form of a mixture of two or more of them.
  • The above-described compound (IV 1'') may be synthesized, for example, by the reaction of a compound (A) (pyromellitic anhydride) represented by the following formula:
    Figure imgb0060
    with at least one compound (B) (p- or m-aminobenzoic acid or an ester thereof, or p- or m-aminophenol or p- or m-acyloxyaniline) represented by the following general formula:
    Figure imgb0061
    wherein
    • m is as difined above,
    • Z bears the same meaning as the above-described Z4 or Z5, and
    • the amino group is present at para or meta position of the benzene nucleus to (̵C )̵m O-Z group.
  • When the above method is employed for the synthesis of the compound (IV 1 ''), the synthesized compound (IV 1 will be generally a mixture of the compound represented by the general formula (IV1 a) and the compound represented by the general formula (IV1 b).
  • The compound (IV 1') may be prepared, for example, by the dehydration-cyclization (imide-cyclization) of the compound (IV 1 synthesized by the above method.
  • Also, the compound (IV 1'') may be prepared by the hydrolysis of the compound (IV 1 ).
  • The reaction of the compound (A) with the compound (B) easily proceeds merely by mixing both compounds, preferably in a molten state, forming a nonsoluble amide acid, i.e. the compound (IV 1 ''), which generally precipitates. Though the reaction proceeds efficiently at room temperature, the preferable reaction temperature ranges from - 50 °C to 100° C, and, in many cases, temperatures of 0 to 80 °C are suitable for the reaction. The reaction proceeds quickly and generally requires no particular catalyst.
  • The dehydration-cyclization of the compound (IV 1 may be carried out by various methods. Some illustrative examples of the methods include (1) a dehydration-cyclization in the presence of a carboxylic anhydride, (2) a dehydration-cyclization using an inorganic acid or a condensation product thereof having dehydrating function, (3) azeotropic dehydration-cyclization in the presence of an acid catalyst, (4) cyclization using a specific dehydration agent, and (5) dehydration-cyclization by heating.
  • Among the compounds (IV 1') those wherein Z4 and Z5 are groups other than hydrogen atom may be prepared by a reaction using the raw material compounds (IV 1 ) each having the corresponding substituent, or may be derived from the compounds (IV 1 wherein Z4 and Z5 are hydrogen atom.
  • When all of the groups Y1, Y2, Y3, Z1, Z2, Z3, Z4, and Z5 in the compounds (I' ), (II'), (III'), and (IV 1') are groups other than hydrogen atom, such compounds may be synthesized individually or simultaneously.
  • The examples of the compound (IV 2" ) include the compounds represented by the following general formulas.
    Figure imgb0062
    Figure imgb0063
    Figure imgb0064
  • These may be used individualy or in a combination of two or more of them.
  • For example, the phthalimide compound (IV 2' ) may be prepared by reacting a derivative of hydroxyphthalic acid represented by the following general formula:
    Figure imgb0065
    wherein Y is Y4 or Y5, and Y4 and Y5 are as defined above and generally are identical with each other, with p-phenylenediamine represented by the following formula:
    Figure imgb0066
    to form the amide acids represented by the above general formulas (IV 2 a), (IV 2 b) or (IV 2 c), followed by dehydrating and cyclizing the obtained amide acids.
  • The reaction of the compound (C) with p-phenylenediamine easily proceeds merely by mixing both the compounds, preferably in a molten state, forming a nonsoluble amide acid which generally precipitates. Though the reaction proceeds efficiently at room temperature, the preferable reaction temperature ranges from - 50 °C to 100°C and in many cases, temperatures of 0 to 80° C are suitable for the reaction. The reaction proceeds quickly and generally requires no particular catalyst.
  • The dehydration-cyclization of the amide acids represented by the formulas (IV 2 a) (IV 2 b), and (IV 2 c) may be carried out by various methods. Some illustrative examples of the methods include those described as the examples of the dehydration-cyclization methods for the compound (IV 1 '').
  • Among the compounds (IV 2' ), those wherein Y4 and Y5 are groups other than hydrogen atom may be prepared by a reaction using the raw material compounds (IV 2" ) each having the corresponding substituent, or may be derived from the compounds (IV 2') wherein Y4 and Y5 are hydrogen atom.
  • When all of the groups Y1, Y2, Y3, Y4, Y5, Z1, Z2, and Z3 in the compounds (I' ), (II' ), (III' ), and (IV 2' ) are groups other than hydrogen atom, such compounds may be synthesized individually or simultaneously.
  • The reaction of the above-described compounds (I ), (II' ), (III' ), and (IV 1') or (IV 2') is carried out generally at 200 to 400 °C preferably 230 to 370° C, generally at atmospheric pressure or below, and in the latter half of the reaction, preferably at a vacuum of 300 to 0.01 Torr. The reaction time varies generally from several minutes to tens of hours depending upon the objective melt viscosity of the polymer. In order to prevent the degradation of the polymer at the reaction temperature, it is preferable to restrict the reaction time to from minutes to hours.
  • Though catalyst is not particularly necessary for the above-described reaction, a proper polycondensation catalyst such as antimony oxide and germanium oxide may be used.
  • Concerning the addition of the reaction materials, all of them may be mixed together from the beginning of the reaction, or each reaction material may be added at a separate reaction stage. For example, the compound (I' ) may be added after the mixture of the compounds (II' ), (III' ), and (IV 1' ) or (IV 2 ) has been reacted to same degree. Such separation in the addition of the reaction materials makes it easier easity to control the distribution of the components of the copolyimide ester, from random copolyester to block copolyester.
  • The reaction is conducted as described above and is concluded by eliminating at least the compound (V' ) (when m is 1), or the compound (VI') and the compound (VII') (when m is 0), or the compound (VIII'
  • The reaction of the compounds (I ), (II'), (III and (IV 1 or (IV 2'') may be carried out by the similar procedure to the reaction of the compounds (I' ), (II' ), (III' ), and (IV 1') or (IV 2') with the exception that the compounds (IV 1 ) or (IV 2' ) are replaced by the compounds (IV 1'') or (IV 2 ) and imidecyclization is further carried out.
  • Though the reaction described above is generally carried out without particular solvent, a suitable solvent may also be used if desired.
  • Thus, the copolyimide ester of the present invention can be prepared. The obtained polymer, if necessary, may be further subjected to after-treatments, such as a known purification, to collect it as a polymer of a desired purity.
  • The copolyimide ester of the present invention can be suitably produced by the above procedure.
  • The copolyimide ester of the present invention may be injection-molded at general molding temperatures (not higher than 400 C) and, also, may be molded by any molding technique employed for molding common thermoplastic resins, such as extrution molding, compression molding, and spinning. Further, the obtained molds may be heat treated at an appropriate temperature for an appropriate time. The copolyimide ester of the present invention is, therefore, a novel thermoplastic polymer which has excellent dimensional stability and dimensional precision in both MD and TD and, as well, excels in heat resistance, mechanical properties, etc. Accordingly, the copolyimide ester of the present invention is useful as materials in various fields, for example, as the material for precision-injection molded parts such as electric or electronic parts which require heat resistance and dimensional precision, filament, film, or sheet.
    • EXAMPLES 1 TO 22 AND COMPARATIVE EXAMPLES 1 TO 5 SYNTHETIC EXAMPLE 1 (1) Synthesis of N,N -bis(4-carboxyphenyl)pyromellitimide
  • Figure imgb0067
  • 39.3 g (0.18 mol) of pyromellitic anhydride and 49.4 g (0.36 mol) of p-aminobenzoic acid were dissolved in 200 ml of dimethylformamide (DMF), and DMF was then refluxed. Directly after beginning the reflux, yellow, powdery crystals started to precipitate. After 2.5 hours of reflux, the reaction mixture was cooled. After filtration of the reaction product, the obtained crystals were washed with successive, DMF and acetone, and were dried to obtain the objective imide (1).
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0068
    • (2) Synthesis of N,N' -bis(4-hydroxyphenyl)pyromellitimide
  • Figure imgb0069
  • 39.3 g (0.18 mol) of pyromellitic anhydride and 39.3 g (0.36 mol) of p-aminophenol were dissolved in 200 ml of dimethylformamide (DMF), and DMF was then refluxed. Directly after beginning the reflux, yellow, platy crystals started to precipitate. After 2.5 hours of reflux, the reaction mixture was cooled. After filtration of the reaction product, the obtained crystals were washed with successive, DMF and acetone, and were dried to obtain the objective imide (2).
  • The results of the elementary analysis of the obtained polymer were as follows:
  • Into a 500 ml separable flask were placed
    • 0.072 mol (9.860 g) of p-aminobenzoic acid,
    • 0.036 mol (7.850 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the amide acid (3) and amide acid (4) represented respectively by the following structural formulas:
    Figure imgb0071
    Figure imgb0072
  • Into the flask were subsequently added
    • 0.600 mol (82.90 g) of p-hydroxybenzoic acid,
    • 0.180 mol (33.52 g) of 4,4 -dihydroxybiphenyl,
    • 0.120 mol (13.21 g) of hydroquinone,
    • 0.204 mol (33.89 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0073
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0074
    Figure imgb0075
    Figure imgb0076
    Figure imgb0077
    Figure imgb0078
    Figure imgb0079
  • The melt viscosity of the polymer was measured with a K o ka-type flow tester (SNIMAZU FLOW TESTER, CFT-500) using a dies of 1.0 mm in diameter and of L/D =10, at a extrusion pressure of 10 kgf/cm2 and at a temperature raising rate of 5°C/min. The polymer had a melt viscosity of 130 Pa•s at 380°C
  • The polymer exhibited optical anisotropy even in molten state. The observation of the optical anisotropy was conducted with a polarizing microscope produced by Nikon Co., Ltd. equipped with a hot stage produced by Lincam Co., Ltd.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 2
  • Into a 500 ml separable flask were placed
    • 0.024 mol (3.291 g) of p-aminobenzoic acid,
    • 0.012 mol (2.617 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (3) and amide acid (4) as those obtained in Example 1.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.240 mol (44.69 g) of 4,4 -dihydroxybiphenyl,
    • 0.168 mol (27.91 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150° C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0080
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0081
    Figure imgb0082
    Figure imgb0083
    Figure imgb0084
    Figure imgb0085
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 75 Paes at 380°C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 3
  • Into a 500 ml separable flask were placed
    • 0.072 mol (9.860 g) of p-aminobenzoic acid,
    • 0.036 mol (7.850 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (3) and amide acid (4) as those obtained in Example 1.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.240 mol (44.69 g) of 4,4 -dihydroxybiphenyl,
    • 0.144 mol (23.92 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0086
  • The infrared spectrum of the obtained polymer is shown in Fig. 1.
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0087
    Figure imgb0088
    Figure imgb0089
    Figure imgb0090
    Figure imgb0091
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 240 Pa•s at 390 C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 4
  • Into a 500 ml separable flask were placed
    • 0.240 mol (32.91 g) of p-aminobenzoic acid,
    • 0.120 mol (26.17 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (3) and amide acid (4) as those obtained in Example 1.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.240 mol (44.69 g) of 4,4 -dihydroxybiphenyl,
    • 0.120 mol (19.94 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0092
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0093
    Figure imgb0094
    Figure imgb0095
    Figure imgb0096
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 150 Pa.s at 320 °C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 5
  • Into a 500 ml separable flask were placed
    • 0.072 mol (9.860 g) of p-aminobenzoic acid,
    • 0.036 mol (7.850 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (3) and amide acid (4) as those obtained in Example 1.
  • Into the flask were subsequently added
    • 0.840 mol (116.0 g) of p-hydroxybenzoic acid,
    • 0.180 mol (33.52 g) of 4,4 -dihydroxybiphenyl,
    • 0.084 mol (13.95 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0097
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0098
    Figure imgb0099
    Figure imgb0100
    Figure imgb0101
    Figure imgb0102
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 215 Pa•s at 380°C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 6
  • Into a 500 ml separable flask were placed
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.240 mol (44.69 g) of 4,4 -dihydroxybiphenyl,
    • 0.144 mol (23.92 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid,
    • 0.036 mol (16.43 g) of N,N' -bis(4-carboxyphenyl)pyromellitimide, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 1500 C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 °C in 90 minutes, and polymerization was then carried out, while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0103
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0104
    Figure imgb0105
    Figure imgb0106
    Figure imgb0107
    Figure imgb0108
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 220 Paes at 380°C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 7
  • Into a 500 ml separable flask were placed
    • 0.720 mol (129.7 g) of p-acetoxybenzoic acid,
    • 0.240 mol (64.87 g) of 4,4 -diacetoxybiphenyl,
    • 0.144 mol (23.92 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 0.036 mol (16.43 g) of N,N -bis(4-carboxyphenyl )pyromellitimide.

    After the mixture was heated to 360 °C in 90 minutes with stirring in a stream of nitrogen, polymerization was carried out while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0109
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0110
    Figure imgb0111
    Figure imgb0112
    Figure imgb0113
    Figure imgb0114
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 175 Pa•s at 380°C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 8
  • Into a 500 ml separable flask were placed
    • 0.072 mol (7.857 g) of p-aminophenol,
    • 0.036 mol (7.852 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the amide acid (5) and amide acid (6) represented respectively by the following structural formulas:
    Figure imgb0115
    Figure imgb0116
  • Into the flask were subsequently added
    • 0.600 mol (82.87 g) of p-hydroxybenzoic acid,
    • 0.144 mol (26.82 g) of 4,4 -dihydroxybiphenyl,
    • 0.120 mol (13.21 g) of hydroquinone,
    • 0.180 mol (29.90 g) of terephthalic acid,
    • 0.120 mol (19.94 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0117
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0118
    Figure imgb0119
    Figure imgb0120
    Figure imgb0121
    Figure imgb0122
    Figure imgb0123
  • The polymer had a melt viscosity of 320 Pa*s at 350° C and exhibited optical anisotropy even in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 9
  • Into a 500 ml separable flask were placed
    • 0.024 mol (2.619 g) of p-aminophenol,
    • 0.012 mol (2.617 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (5) and amide acid (6) as those obtained in Example 8.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.228 mol (42.46 g) of dihydroxybiphenyl,
    • 0.180 mol (29.90 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150° C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0124
  • The infrared spectrum of the obtained polymer is shown in Fig. 2.
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0125
    Figure imgb0126
    Figure imgb0127
    Figure imgb0128
    Figure imgb0129
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 230 Pa•s at 380°C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 10
  • Into a 500 ml separable flask were placed
    • 0.072 mol (7.857 g) of p-aminophenol,
    • 0.036 mol (7.852 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (5) and amide acid (6) as those obtained in Example 8.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.204 mol (37.99 g) of dihydroxybiphenyl,
    • 0.120 mol (19.94 g) of terephthalic acid,
    • 0.120 mol (19.94 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0130
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0131
    Figure imgb0132
    Figure imgb0133
    Figure imgb0134
    Figure imgb0135
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 170 Paes at 330°C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 11
  • Into a 500 ml separable flask were placed
    • 0.240 mol (26.19 g) of p-aminophenol,
    • 0.120 mol (26.17 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (5) and amide acid (6) as those obtained in Example 8.
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.12 mol (22.35 g) of dihydroxybiphenyl,
    • 0.240mol (39.88 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360°C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0136
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0137
    Figure imgb0138
    Figure imgb0139
    Figure imgb0140
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 210 Paes at 320 °C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 12
  • Into a 500 ml separable flask were placed
    • 0.072 mol (7.857 g) of p-aminophenol,
    • 0.036 mol (7.852 g) of pyromellitic anhydride, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the same amide acid (5) and amide acid (6) as those obtained in Example 8.
  • Into the flask were subsequently added
    • 0.84 mol (116.0 g) of p-hydroxybenzoic acid,
    • 0.144 mol (26.82 g) of dihydroxybiphenyl,
    • 0.060 mol (9.968 g) of terephthalic acid,
    • 0.120 mol (19.94 g) of isophthalic acid, and

    1.200 mol (112.8 ml) of acetic anhydride. After the mixture was heated to 150° C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0141
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0142
    Figure imgb0143
    Figure imgb0144
    Figure imgb0145
    Figure imgb0146
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 180 Paes at 32 C
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 13
  • Into a 500 ml separable flask were placed
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.204 mol (37.99 g) of dihydroxybiphenyl,
    • 0.120 mol (19.94 g) of terephthalic acid,
    • 0.120 mol (19.94 g) of isophthalic acid,
    • 0.036 mol (14.41 g) of N,N -bis(4-hydroxyphenyl)pyromellitimide, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360°C in 90 minutes, and polymerization were then carried out, while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0147
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0148
    Figure imgb0149
    Figure imgb0150
    Figure imgb0151
    Figure imgb0152
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 200 Pa·s at 330°C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • EXAMPLE 14
  • Into a 500 ml separable flask were placed
    • 0.720 mol (129.7 g) of p-acetoxybenzoic acid,
    • 0.204 mol (55.14 g) of 4,4 -diacetoxybiphenyl,
    • 0.120 mol (19.94 g) of terephthalic acid,
    • 0.120 mol (19.94 g) of isophthalic acid, and
    • 0.036 mol (17.44 g) of N,N' -bis(4-acetoxyphenyl)pyromellitimide.

    After the mixture was heated to 360 °C in 90 minutes with stirring in a stream of nitrogen, polymerization was carried out while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0153
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0154
    Figure imgb0155
    Figure imgb0156
    Figure imgb0157
    Figure imgb0158
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 140 Paes at 340°C.
  • The polymer exhibited optical anisotropy in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described later. The results are shown in the Table 1.
    • COMPARATIVE EXAMPLES 1 TO 5
  • In each Comparative Example, the measurement procedures of Example 1 were repeated with the exception that the copolyimide ester prepared in Example 1 was replaced by a commercial poly- butyleneterephthalate (Duranex 2000 produced by Celanese Co., Ltd., Comparative Example 1), a commercial polycarbonate (A 2200 produced by Idemitsu Petrochemical Co., Ltd., Comparative Example 2), a commercial polyether imide (Ultem 1000 produced by General Electric Company, Comparative Example 3), a commercial thermotropic iiquid-crystalline copolyester (Ekonol E 6000 produced by SUMITOMO CHEMICAL CO., LTD., Comparative Example 4), or a commercial thermotropic liquid-crystalline copolyester (Vectra A 950 produced by Celanese Co., Ltd., Comparative Example 5), respectively.
  • The results are shown in Table 1.
    Figure imgb0159
  • The measurement of the coefficient of linear expansion, coefficient of mold shrinkage, flexural properties, and heat distortion temperatures was conducted as follows.
    • Molding of test piece
  • The molding was conducted by using an injection molder (Toshiba IS 45 P) at a molding temperature of 250 to 350 C and at a mold temperature of 120" C
    • Measuring methods 1. Coefficient of linear expansion
  • The measurement of coefficient of linear expansion was conducted in compression mode by using Seiko Thermal Analysis Apparatuses SSC-300 and TMA-100 on a test piece of about 10 (measuring direction)x 5x 1.6 mm cut out from the center portion of a plate of 63.5x 63.5x 1.6 mm, under a load of 5 g, at a temperature raising rate of 10°C /min.
    • 2. Coefficient of mold shrinkage
  • The coefficients of mold shrinkage in MD and TD of the plate described above were calculated by the following formula.
  • Coefficient of mold shrinkage = [ (Inner size of mold cavity) - (Measured length of test piece) /(Inner size of mold cavity)]x 100 (%)
    • 3. Flexural properties
  • The measurement of flexural properties was conducted on a test piece of 127x 12.7x 3.2 mm at 23°C using HTM 250 produced by Toyo Seiki Co., Ltd.
  • The other conditions were accordant to ASTM-D-790.
    • 4. Heat distortion temperature
  • The measurement of heat distortion temperature was conducted on a test piece of 127x 12. 7x 3.2 mm under a load of 18.6 kg/cm2 using an apparatus produced by Toyo Seiki Co., Ltd.
  • The other test conditions were accordant to ASTM-D-648.
    • SYNTHETIC EXAMPLE 2 Synthesis of the compound (IV 2 )
  • Figure imgb0160
  • 59.08 g (0.36 mol) of hydroxyphthalic anhydride and 19.47 g (0.18 mol) of p-phenylenediamine were dissolved in 200 ml of dimethylformamide (DMF), and DMF was then refluxed. Directly after beginning the reflux, yellow, powdery crystals started to precipitate. After 2.5 hours of reflux, the reaction mixture was cooled. After filtration of the reaction product, the obtained crystals were washed with successive, DMF and acetone, and were dried to obtain the objective compound (IV2 ).
  • The results of the elementary analysis of the obtained compound were as follows:
    Figure imgb0161
    • EXAMPLE 15
  • Into a 500 ml separable flask were placed
    • 0.024 mol (3.939 g) of hydroxyphthalic anhydride,
    • 0.012 mol (1.298 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2" ) (Y4 and Y5: H).
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.120 mol (22.34 g) of 4,4 -dihydroxybiphenyl,
    • 0.108 mol (11.89 g) of hydroquinone,
    • 0.180 mol (29.90 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 ° C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0162
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0163
    Figure imgb0164
    Figure imgb0165
    Figure imgb0166
    Figure imgb0167
    Figure imgb0168
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 280 Paes at 380°C
  • The polymer exhibited optical anisotropy even in molten state.
  • The coefficient of linear expansion, coefficient of mold shrinkage, flexural strength, flexural modulus, and heat distortion temperature of the polymer were measured according to the methods described above. The results are shown in the Table 2.
    • EXAMPLE 16
  • Into a 500 ml separable flask were placed
    • 0.240 mol (39.39 g) of hydroxyphthalic anhydride,
    • 0.120 mol (12.98 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2" ) (Y4 and Y5: H).
  • Into the flask were subsequently added
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.120 mol (22.34 g) of 4,4 -dihydroxybiphenyl,
    • 0.144 mol (23.92 g) of terephthalic acid,
    • 0.096 mol (15.95 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150 °C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0169
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0170
    Figure imgb0171
    Figure imgb0172
    Figure imgb0173
    Figure imgb0174
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 340 Pa·s at 380 C . The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 17
  • Into a 500 ml separable flask were placed
    • 0.024 mol (3.939 g) of hydroxyphthalic anhydride,
    • 0.012 mol (1.298 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2") (Y4 and YS : H).
  • Into the flask were subsequently added
    • 0.600 mol (82.87 g) of p-hydroxybenzoic acid,
    • 0.288 mol (53.63 g) of 4,4' -dihydroxybiphenyl,
    • 0.240 mol (39.87 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150° C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0175
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0176
    Figure imgb0177
    Figure imgb0178
    Figure imgb0179
    Figure imgb0180
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 300 Pass at 380 °C. The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 18
  • Into a 500 ml separable flask were placed
    • 0.240 mol (39.39 g) of hydroxyphthalic anhydride,
    • 0.120 mol (12.98 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2" ) (Y4 and Y5: H).
  • Into the flask were subsequently added
    • 0.600 mol (82.87 g) of p-hydroxybenzoic acid,
    • 0.180 mol (33.52 g) of 4,4 -dihydroxybiphenyl,
    • 0.204 mol (33.89 g) of terephthalic acid,
    • 0.096 mol (15.95 g) of isophthalic acid, and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150° C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 °C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0181
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0182
    Figure imgb0183
    Figure imgb0184
    Figure imgb0185
    Figure imgb0186
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 380 Pa·s at 380°C . The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 19
  • Into a 500 ml separable flask were placed
    • 0.024 mol (3.939 g) of hydroxyphthalic anhydride,
    • 0.012 mol (1.298 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2" ) (Y4 and Ys: H).
  • Into the flask were subsequently added
    • 0.84 mol (116.0 g) of p-hydroxybenzoic acid,
    • 0.168 mol (31.28 g) of 4,4 -dihydroxybiphenyl,
    • 0.12 mol (19.94 g) of terephthalic acid,
    • 0.060mol (9.968 g) of isophthalic acid, and
    • 1.200mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360°C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0187
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0188
    Figure imgb0189
    Figure imgb0190
    Figure imgb0191
    Figure imgb0192
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 270 Pa·s at 380 C . The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 20
  • Into a 500 ml separable flask were placed
    • 0.240 mol (39.90 g) of hydroxyphthalic anhydride,
    • 0.120 mol (12.98 g) of p-phenylenediamine, and
    • 100 ml of methyl ethyl ketone,

    and the mixture was stirred for one hour at room temperature, to form the precipitate of the compound (IV 2" )(Y4 and YS: H).
  • Into the flask were subsequently added
    • 0.840 mol (116.0 g) of p-hydroxybenzoic acid,
    • 0.060 mol (11.17 g) of 4,4 -dihydroxybiphenyl,
    • 0.084 mol (13.95 g) of terephthalic acid,
    • 0.096 mol (15.95 g) of isophthalic acid, and
    • 1.200mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 C in 90 minutes, and the dehydration-cyclization of the amide acids and polymerization were carried out, while distilling methyl ethyl ketone, water, and acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0193
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0194
    Figure imgb0195
    Figure imgb0196
    Figure imgb0197
    Figure imgb0198
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 370 Pa·s at 380 °C. The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 21
  • Into a 500 ml separable flask were placed
    • 0.720 mol (99.45 g) of p-hydroxybenzoic acid,
    • 0.204 mol (37.99 g) of 4,4 -dihydroxybiphenyl,
    • 0.180 mol (29.90 g) of terephthalic acid,
    • 0.060 mol (9.968 g) of isophthalic acid,
    • 0.036 mol (14.41 g) of the compound (IV 2' )(Y4 and Y5: H), and
    • 1.200 mol (112.8 ml) of acetic anhydride.

    After the mixture was heated to 150°C with stirring in a stream of nitrogen, acetic anhydride was refluxed for one hour. Subsequently, the temperature was raised to 360 °C in 90 minutes, and polymerization were then carried out, while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0199
  • The infrared spectrum of the obtained polymer is shown in Fig. 3.
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0200
    Figure imgb0201
    Figure imgb0202
    Figure imgb0203
    Figure imgb0204
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 300 Pa·s at 380 °C . The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    • EXAMPLE 22
  • Into a 500 ml separable flask were placed
    • 0.720 mol (129.7 g) of p-acetoxybenzoic acid,
    • 0. 204 mol (55.14 g) of 4,4 -diacetoxybiphenyl,
    • 0.180 mol (29.90 g) of terephthalic acid,
    • 0 060 (9.968 g) of isophthalic acid, and
    • 0.036 mol (14.41 g) of the compound (IV 2' )(Y4 and Ys: H).

    After the mixture was heated to 360 °C in 90 minutes with stirring in a stream of nitrogen, polymerization was carried out while distilling acetic acid out. After the pressure of the reaction system was reduced to 10 torr, the polymerization was continued for 10 minutes and was then continued further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was collected in a form of molten state.
  • The results of the elementary analysis of the obtained polymer were as follows:
    Figure imgb0205
  • From these results, the polymer was identified to be a copolyimide ester having the structural units and the composition represented by the following formulas.
    Figure imgb0206
    Figure imgb0207
    Figure imgb0208
    Figure imgb0209
    Figure imgb0210
  • The melt viscosity of the polymer was measured by the same method as Example 1 to be 310 Pa·s at 380 °C. The properties of the polymer are shown in Table 2.
  • The polymer exhibited optical anisotropy in molten state.
    Figure imgb0211
  • In the Examples 15 to 22, molding of the test pieces was carried out by the same method as that employed in Examples 1 to 14.
  • The measurement of the coefficient of linear expansion, coefficient of mold shrinkage, flexural properties and heat distortion temperature was conducted by the same way as of Examples 1 to 14.

Claims (9)

1. A thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0212
the recurring unit (II) represented by the following general formula:
Figure imgb0213
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0214
wherein
the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring units (IV 1) or (IV 2) represented respectively by the following general formulas;
Figure imgb0215
wherein
-Q- is -O- or -CO-
and each Q is present at para position or meta position of the benzene nucleus respectively to the imide group,
or
Figure imgb0216
with the proviso that the recurring units (I), (II), (III), and (IV 1) er (IV 2) are bonded to form ester bonds, and wherein the thermoplastic wholly aromatic copolyimide ester has a melt viscosity of from 1.0 to 1.0 x 105 Pa·s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400°C
2. The thermoplastic wholly aromatic copolyimide ester of claim 1 consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0217
the recurring unit (II) represented by the following general formula:
Figure imgb0218
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0219
 wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 1) represented by the following general formula;
Figure imgb0220
wherein
-Q- is -O- or -CO-
and each Q is present at para position or meta position of the benzene nucleus respectively to the imide group,
and wherein when -Q- is -CO-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (III)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(III)+(IV 1)] is from (10/11) to (11/10), and when -Q- is -O-, then the mole ratio of (1)/[(II)+(III)+(IV 1)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II)+(IV 1)] is from (10/11) to (11/10).
3. The thermoplastic wholly aromatic copolyimide ester of claim 2 consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0221
the recurring unit (II) represented by the following formula:
Figure imgb0222
two kinds of the recurring units (III) represented respectively by the following formulas:
Figure imgb0223
and
Figure imgb0224
and the recurring unit (IV 1) represented by the following formula:
Figure imgb0225
and wherein the thermoplastic wholly aromatic copolyimide ester contains 2 to 22 mol % of the recurring unit (III) represented by the following formula:
Figure imgb0226
4. The thermoplastic wholly aromatic copolyimide ester of claim 2 consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0227
the recurring unit (II) represented by the following formula:
Figure imgb0228
two kinds of the recurring units (III) represented respectively by the following formulas:
Figure imgb0229
and
Figure imgb0230
and the recurring unit (IV 1) represented by the following formula:
Figure imgb0231
and wherein the thermoplastic wholly aromatic copolyimide ester contains 2 to 22 mol % of the recurring unit (III) represented by the following formula:
Figure imgb0232
5. The thermoplastic wholly aromatic copolyimide ester of claim 1 consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0233
the recurring unit (II) represented by the following general formula:
Figure imgb0234
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0235
wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 2) represented by the following general formula:
Figure imgb0236
and wherein the mole ratio of (I)/[(II) + (III) + (IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II)+(IV 2)] is from (10/11) to (11/10).
6. A process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0237
the recurring unit (II) represented by the following formula:
Figure imgb0238
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0239
wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 1) represented by the following general formula:
Figure imgb0240
wherein
-Q- is -0- or -CO-
and each Q is present at para position or meta position of the benzene nucleus respectively to the imide group;
with the proviso that the recurring units (I), (II), (III), and (IV 1) are bonded to form ester bonds and that when -Q-is -CO-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (III)-/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(III)+(IV 1)] is from (10/11) to (11/10), and when -Q- is -0-, then the mole ratio of (I)/[(II) + (III) +(IV 1)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II) + (IV 1)] is from (10/11) to (11/10);
and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pass as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400°C. which process comprises:
reacting a compound (I') represented by the following general formula:
Figure imgb0241
wherein
Y' is hydrogen atom or R1 CO-, R1 being a hydrocarbon group of 1 to 18 carbon atoms, and Z1 is hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms;
a compound (II') represented by the following general formula:
Figure imgb0242
wherein
n is an integer of 0 or 1,
Y2 is hydrogen atom or R2CO-, and
Y3 is hydrogen atom or R3CO-,
R2 and R3 being independently a hydrocarbon group of 1 to 18 carbon atoms; a compound (III') represented by the following general formula:
Figure imgb0243
wherein
Z2 and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and the - C - O-Z3 group is present at para position or meta position of the benzene nucleus to the Z2-0- C - group;
and the compound (IV 1') represented by the following general formula:
Figure imgb0244
wherein
m is an integer of 0 or 1,
Z4 is, when m=0, hydrogen atom or R4-CO-, R4 being a hydrocarbon group of 1 to 18 carbon atoms or, when m = 1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms,
Z5 is, when m=0, hydrogen atom or RS-CO-, R5 being a hydrocarbon group of 1 to 18 carbon atoms or, when m = 1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, Z4-O(̵C )̵m is present at para position or meta position of the benzene nucleus to the imide group, and (̵C)̵mO-Z5 is present at para position or meta position of the benzene nucleus to the imide group;
in such amounts as satisfy, when m = 1, a mole ratio of (I' )/((II') + (III' ) + (IV 1' )] of from (20/80) to (90/10), a mole ratio of (III' )/(IV 1' ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (II' )/[(III' ) + (IV 1 )] of from (10/11) to (11/10) or, when m=0, a mole ratio of (I' )/[(II' ) + (III' ) + (IV 1' )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 1' ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (II' )/[(II' ) + (IV 1' )] of from (10/11) to (11/10), so that when m=1, then a compound (V') represented by the following general formula:
Yp-O-Zq (V')

wherein
YP is Y1, Y2 or Y3 and Zq is Z1, Z2 , Z3, Z4 or Z5,
is eliminated,
or, when m = 0, then a compound (VI' ) represented by the following general formula:
Yp-O-Zs (VI' )

wherein
YP is as defined above and
Zs is Z1, Z2 or Z3,
and a compound (VII' ) represented by the following general formula:
Zr-O-Zs (VII' )

wherein
ZS is as defined above,
and Z' is Z4 or Z5,

are eliminated.
7. A process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0245
the recurring unit (II) represented by the following general formula:
Figure imgb0246
 wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0247
wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 1) represented by the following general formula:
Figure imgb0248
wherein
-Q- is -0- or -CO-
and each Q is present at para position or meta position of the benzene nucleus respectively to the imide groups;
with the proviso that the recurring units (I), (II), (III), and (IV 1) are bonded to form ester bonds and that when -Q-is -CO-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (III)-/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (II)/[(I II) + (IV 1)] is from (10/11) to (11/10), and when -Q- is -0-, then the mole ratio of (I)/[(II) + (III) + (IV 1)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 1) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II) + (IV 1)] is from (10/11) to (11/10);
and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa·s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400°C, which process comprises:
reacting a compound (I' ) represented by the following general formula:
Figure imgb0249
wherein
Y1 is hydrogen atom or R1CO-, R1 being a hydrocarbon group of 1 to 18 carbon atoms, and
Z1 is hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms;
a compound (II' ) represented by the following general formula:
Figure imgb0250
wherein
n is an integer of 0 or 1,
Y2 is hydrogen atom or R2CO-, and
Y3 is hydrogen atom or R3CO-,
R2 and R3 being independently a hydrocarbon group of 1 to 18 carbon atoms;
a compound (III ) represented by the following general formula:
Figure imgb0251
wherein
Z2 and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and the - C - O-Z3 O group is present at para position or meta position of the benzene nucleus to the Z2-0- C - group;
and a compound (IV 1" ) represented by the following general formulas:
Figure imgb0252
Figure imgb0253
wherein
m is an integer of 0 or 1,
Z4 when m=0, hydrogen atom or R4-CO-, R4 being a hydrocarbon group of 1 to 18 carbon atoms or, when m=1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms,
Z5 is, when m=0, hydrogen atom or R5-CO-, R5 being a hydrocarbon group of 1 to 18 carbon atoms or, when m = 1, hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, Z4-O(̵ C )̵m is present at para position or meta position of the benzene nucleus to the amido group, and (̵C )̵m O-Z5 is present at para position or meta position of the benzene nucleus to the amido group;
in such amounts as satisfy, when m=1, a mole ratio of (I )/[(II" ) + (III + (IV 1 )] of from (20/80) to (90/10), a mole ratio of (III' )/(IV 1" ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (II' )/[(III' ) + (IV 1" )] of from (10/11) to (11/10) or, when m=0, a mole ratio of (I' )/[(II' ) + (III' ) + (IV 1" )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 1" ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III )/[(II' ) + (IV 1")] of from (10/11) to (11 /10),
so that the compound (IV 1" ) is imide-cyclized and, when m is 1, then a compound (V') represented by the following general formula:
YP-O-Zq (V)

wherein
YP is Y1, Y2 or Y3 and
Zq is Z1, Z2, Z3, Z4 or Z5,

is eliminated,
or, when m is 0, then a compound (VI' ) represented by the following general formula: Yp-O-Zs NI' )

wherein
YP is as defined above and
Zs is Z1, Z2 or Z3,
and a compound (VII' ) represented by the following general formula:
Zr-O-Zs (vII' )

wherein
ZS is as defined above and
Zr is Z4 or Z5,

are eliminated.
8. A process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0254
the recurring unit (II) represented by the following general formula:
Figure imgb0255
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0256
wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 2) represented by the following formula;
Figure imgb0257
with the proviso that the recurring units (I), (II), (III), and (IV 2) are bonded to form ester bonds and that the mole ratio of (I)/[(II) + (III) + (IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II) + (IV 2)] is from (10/11) to (11/10);
and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Paes as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400 ° C, which process comprises:
reacting a compound (I' ) represented by the following general formula:
Figure imgb0258
wherein
Y1 is hydrogen atom or R1CO- , R1 being a hydrocarbon group of 1 to 18 carbon atoms, and
Z1 is hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms;
a compound (II' ) represented by the following general formula:
Figure imgb0259
wherein
n is an integer of 0 or 1,
Y2 is hydrogen atom or R2CO-, and
Y3 is hydrogen atom or R3CO-,
R2 and R3 being independently a hydrocarbon group of 1 to 18 carbon atoms; a compound (III' ) represented by the following general formula:
Figure imgb0260
wherein
Z2 and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and the - C - O-Z3 group is present at para position or meta position of the benzene nucleus to the Z2-0- C - 0 group;
and the compound (IV 2 ) represented by the following general formula:
Figure imgb0261
wherein
Y4 is hydrogen atom or R6-CO- and
Y5 is hydrogen atom or R7-CO-, R6 and R7 being independently a hydrocarbon group of 1 to 18 carbon atoms;
in such amounts as satisfy a mole ratio of (I' )/[(II' ) + (III' ) + (IV 2' )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 2' ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III )/[(II' ) + (IV 2' )] of from (10/11) to (11/10),
so that a compound (VIII' ) represented by the following general formula:
Yt-O-Zu (VIII' )

wherein
Yt is Y1, Y2, Y3, Y4 or Y5 and
Zu is Z1, Z2, or Z3,

is eliminated.
9. A process for producing a thermoplastic wholly aromatic copolyimide ester consisting essentially of the recurring unit (I) represented by the following formula:
Figure imgb0262
the recurring unit (II) represented by the following general formula:
Figure imgb0263
wherein
n is an integer of 0 or 1;
the recurring unit (III) represented by the following formula:
Figure imgb0264
wherein the two carbonyl groups are present at para position or meta position of the benzene nucleus to each other;
and the recurring unit (IV 2) represented by the following formula:
Figure imgb0265
with the proviso that the recurring units (I), (II), (III), and (IV 2) are bonded to form ester bonds and that the mole ratio of (I)/[(II) + (I11);(IV 2)] is from (20/80) to (90/10), the mole ratio of (II)/(IV 2) is from (0.1/99.9) to (99.9/0.1), and the mole ratio of (III)/[(II) + (IV 2)] is from (10/11) to (11/10);
and the thermoplastic wholly aromatic copolyimide ester having a melt viscosity of from 1.0 to 1.0 x 105 Pa·s as measured at a shear stress of 0.025 Mpa and at a temperature of from 300 to 400°C, which process comprises:
reacting a compound (I' ) represented by the following general formula:
Figure imgb0266
wherein
Y1 is hydrogen atom or R1CO- , R1 being a hydrocarbon group of 1 to 18 carbon atoms, and
Z1 is hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms;
a compound (II' ) represented by the following general formula:
Figure imgb0267
wherein
n is an integer of 0 or 1,
Y2 hydrogen atom or R2CO-, and
Y3 hydrogen atom or R3CO-,
R2 and R3 being independently a hydrocarbon group of 1 to 18 carbon atoms;
a compound (III' ) represented by the following general formula:
Figure imgb0268
wherein
Z2 and Z3 are independently hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, and the - C - 0-Z3 group is present at para position or meta position of the benzene nucleus to the Z2-0- group;
and a compound (IV 2 ) represented by the following general formula:
Figure imgb0269
wherein
Y4 is hydrogen atom or R6-CO-,
Y5 is hydrogen atom or R7-CO-, R6 and R7 being independently a hydrocarbon group of 1 to 18 carbon atoms, and
each Y4O- and -OY5 is present at para position or meta position of the benzene nucleus respectively to the amido group;
in such amounts as satisfy a mole ratio of (I' )/[(II' ) + (III' ) + (IV 2" )] of from (20/80) to (90/10), a mole ratio of (II' )/(IV 2" ) of from (0.1/99.9) to (99.9/0.1), and a mole ratio of (III' )/[(II' ) + (IV" )] of from (10/11) to (11/10),
so that the compound (IV 2" ) is imide-cyclized and a compound (VIII' ) represented by the following general formula:
Yt-O-Zu (VIII' ) wherein
Yt is Y1, Y2, Y3, Y4 or Y5 and Zu is Z1, Z2 or Z3,
is eliminated.
EP89108880A 1988-05-17 1989-05-17 Thermoplastic wholly aromatic copolyimide ester and process for producing the same Expired - Lifetime EP0342652B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544159A2 (en) * 1991-11-26 1993-06-02 BASF Aktiengesellschaft High temperature resistant bloc-copolycondensates
US6479950B2 (en) 1999-12-22 2002-11-12 Matsushita Electric Industrial Co., Ltd. High intensity discharge lamp, driving apparatus for high intensity discharge lamp, and high intensity discharge lamp system

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166308A (en) * 1990-04-30 1992-11-24 E. I. Du Pont De Nemours And Company Copolyimide film with improved properties
JP4940522B2 (en) 2001-09-10 2012-05-30 住友化学株式会社 Totally aromatic polyimide ester and method for producing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076482A1 (en) * 1981-10-02 1983-04-13 E.I. Du Pont De Nemours And Company Elastomeric polyetheresterimides
JPS62132929A (en) * 1985-12-06 1987-06-16 Idemitsu Kosan Co Ltd Novel polymer and production thereof
EP0252415A2 (en) * 1986-07-07 1988-01-13 Idemitsu Kosan Company Limited Novel polyester polymers

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3542731A (en) * 1969-10-02 1970-11-24 Ashland Oil Inc Heterocyclic aromatic polyesters
US4161470A (en) * 1977-10-20 1979-07-17 Celanese Corporation Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing
US4176223A (en) * 1978-12-18 1979-11-27 E. I. Du Pont De Nemours And Company Polyimide-esters and filaments prepared from 4-(4'-carboxyphthalimido)benzoic acid or 4-(4'-hydroxyphthalimido)phenol
JPS5867725A (en) * 1981-10-19 1983-04-22 Mitsui Toatsu Chem Inc Polyimide ester and its preparation
US4383105A (en) * 1981-12-28 1983-05-10 E. I. Du Pont De Nemours And Company Polyimide-esters and filaments
JPS604531A (en) * 1983-06-23 1985-01-11 Mitsubishi Chem Ind Ltd Polyester imide having high rigidity
EP0294195B1 (en) * 1987-06-05 1993-11-24 MITSUI TOATSU CHEMICALS, Inc. Polyimide resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076482A1 (en) * 1981-10-02 1983-04-13 E.I. Du Pont De Nemours And Company Elastomeric polyetheresterimides
JPS62132929A (en) * 1985-12-06 1987-06-16 Idemitsu Kosan Co Ltd Novel polymer and production thereof
EP0252415A2 (en) * 1986-07-07 1988-01-13 Idemitsu Kosan Company Limited Novel polyester polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 361 (C-459)(1808) 25 November 1987, & JP-A-62 132929 (IDEMITSU KOSAN CO LTD) 16 June 1987, *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544159A2 (en) * 1991-11-26 1993-06-02 BASF Aktiengesellschaft High temperature resistant bloc-copolycondensates
EP0544159A3 (en) * 1991-11-26 1993-10-13 Basf Aktiengesellschaft High temperature resistant bloc-copolycondensates
US6479950B2 (en) 1999-12-22 2002-11-12 Matsushita Electric Industrial Co., Ltd. High intensity discharge lamp, driving apparatus for high intensity discharge lamp, and high intensity discharge lamp system

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